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排序方式: 共有893条查询结果,搜索用时 31 毫秒
41.
Alicia M. Phelps Nicholas S. Dolan Nathan T. Connell Jennifer M. Schomaker 《Tetrahedron》2013,69(27-28):5614-5621
A versatile intramolecular reaction of allene-containing diazomalonates that exhibits excellent chemoselectivity for either allenic C–H insertion or cyclopropanation is demonstrated. The identity of the product depends on the transition metal catalyst that is employed for the reaction. Rh catalysts promote exclusive C–H insertion with good diastereoselectivity for the trans product, while Cu catalysis enables intramolecular cyclopropanation to yield methylenecyclopropanes with moderate to good E:Z ratios. 相似文献
42.
Alicia Monleón Prof. Dr. Gonzalo Blay Prof. Dr. Luis R. Domingo Prof. Dr. M. Carmen Muñoz Prof. Dr. José R. Pedro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14852-14860
A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I2, Br2 and Cl2 as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed. 相似文献
43.
Eric Iván Sánchez‐Flores Rodrigo Chávez‐Calvillo Todd A. Keith Gabriel Cuevas Tomás Rocha‐Rinza Fernando Cortés‐Guzmán 《Journal of computational chemistry》2014,35(10):820-828
The topological analysis of the electron density for electronic excited states under the formalism of the quantum theory of atoms in molecules using time‐dependent density functional theory (TDDFT) is presented. Relaxed electron densities for electronic excited states are computed by solving a Z‐vector equation which is obtained by means of the Sternheimer interchange method. This is in contrast to previous work in which the electron density for excited states is obtained using DFT instead of TDDFT, that is, through the imposition of molecular occupancies in accordance with the electron configuration of the excited state under consideration. Once the electron density of the excited state is computed, its topological characterization and the properties of the atoms in molecules are obtained in the same manner that for the ground state. The analysis of the low‐lying singlet and triplet vertical excitations of CO and C6H6 are used as representative examples of the application of this methodology. Altogether, it is shown how this procedure provides insights on the changes of the electron density following photoexcitation and it is our hope that it will be useful in the study of different photophysical and photochemical processes. © 2014 Wiley Periodicals, Inc. 相似文献
44.
Ionic liquids (ILs) are considered to be one of the steppingstones to fabricate next generation electrochemical devices given their unique physical and chemical properties. The addition of water to ILs significantly impact electrochemical related properties including viscosity, density, conductivity, and electrochemical window. Herein we utilize ambient pressure X-ray photoelectron spectroscopy (APXPS) to examine the impact of water on values of the electrochemical shift (S), which is determined by measuring changes in binding energy shifts as a function of an external bias. APXPS spectra of C 1s, O 1s and N 1s regions are examined for the IL 1-butyl-3-methylimidazolium acetate, [C4mim][OAc], at the IL/gas interface as a function of both water vapor pressure and external bias. Results reveal that in the absence of water vapor there is an IL ohmic drop between the working electrode and quasi reference electrode, giving rise to chemical specific S values of less than one. Upon introducing water vapor, S values approach one as a function of increasing water vapor pressure, indicating a decrease in the IL ohmic drop as the IL/water mixture becomes more conductive and the potential drop is driven by the electric double layer at the electrode/IL interface. 相似文献
45.
Dr. Philip Junker Alicia Rey Planells Prof. Dr. Arturo Espinosa Ferao Prof. Dr. Rainer Streubel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9350-9359
Several phosphaquinodimethanes and their M(CO)5 complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH2 substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8. 相似文献
46.
Imaging the Magnetic Reversal of Isolated and Organized Molecular‐Based Nanoparticles using Magnetic Force Microscopy
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Elena Pinilla‐Cienfuegos Samuel Mañas‐Valero Josep Canet‐Ferrer Laure Catala Talal Mallah Alicia Forment‐Aliaga Eugenio Coronado 《Particle & Particle Systems Characterization》2015,32(6):693-700
In the race towards miniaturization in nanoelectronics, magnetic nanoparticles (MNPs) have emerged as potential candidates for their integration in ultrahigh‐density recording media. Molecular‐based materials open the possibility to design new tailor‐made MNPs with variable composition and sizes, which benefit from the intrinsic properties of these materials. Before their implementation in real devices is reached, a precise organization on surfaces and a reliable characterization and manipulation of their individual magnetic behavior are required. In this paper, it is demonstrated how molecular‐based MNPs are accurately organized on surfaces and how the magnetic properties of the individual MNPs are detected and tuned by means of low‐temperature magnetic force microscopy (LT‐MFM) with variable magnetic field. The magnetization reversal on isolated and organized MNPs is investigated; in addition, the temperature dependence of their magnetic response is evaluated. 相似文献
47.
Silicon nitride/silicon oxide interlayers for solar cell passivating contacts based on PECVD amorphous silicon
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This Letter demonstrates improved passivating contacts for silicon solar cells consisting of doped silicon films together with tunnelling dielectric layers. An improvement is demonstrated by replacing the commonly used silicon oxide interfacial layer with a silicon nitride/silicon oxide double interfacial layer. The paper describes the optimization of such contacts, including doping of a PECVD intrinsic a‐Si:H film by means of a thermal POCl3 diffusion process and an exploration of the effect of the refractive index of the SiNx. The n+ silicon passivating contact with SiNx /SiOx double layer achieves a better result than a single SiNx or SiOx layer, giving a recombination current parameter of ~7 fA/cm2 and a contact resistivity of ~0.005 Ω cm2, respectively. These self‐passivating electron‐selective contacts open the way to high efficiency silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
48.
Nickel‐Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products
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Sarah Z. Tasker Dr. Alicia C. Gutierrez Prof. Timothy F. Jamison 《Angewandte Chemie (International ed. in English)》2014,53(7):1858-1861
Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel‐catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity. 相似文献
49.
Ross F. Koby Alicia M. Doerr Nicholas R. Rightmire Nathan D. Schley Brian K. Long Timothy P. Hanusa 《Angewandte Chemie (International ed. in English)》2020,59(24):9542-9548
Milling two equivalents of K[1,3‐(SiMe3)2C3H3] (=K[A′]) with MgX2 (X=Cl, Br) produces the allyl complex [K2MgA′4] ( 1 ). Crystals grown from toluene are of the solvated species [((η6‐tol)K)2MgA′4] ([ 1 ?2(tol)]), a trimetallic monomer with both bridging and terminal (η1) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C?C bond lengths differ by only 0.028 Å, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an η3‐allyl configuration on Mg is energetically preferred over the η1‐ (σ‐bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1 , with activities that are comparable to K[A′] and greater than the homometallic magnesium complex [{MgA′2}2]. 相似文献
50.
Ewan Couic Alicia Tribondeau Vanessa Alphonse Alexandre Livet Noureddine Bousserrhine 《Molecules (Basel, Switzerland)》2022,27(6)
Understanding ecological trajectories after mine site rehabilitation is essential to develop relevant protocols adapted for gold mining sites. This study describes the influence of a range of mine site rehabilitation and revegetation protocols on soil physicochemical parameters and microbial activities related to carbon, nitrogen and phosphorus cycles. We sampled soil from six rehabilitated mining sites in French Guiana with different plant cover (herbaceous, Cyperaceous, monoculture of Clitoria racemosa and Acacia mangium and association of C. racemosa and A. mangium). We measured the mineralization potential of organic matter by estimating the mineralization of carbon, nitrogen and phosphorus and the microbial catabolic diversity balance. The results showed an improvement in the quality of organic matter on revegetated sites with tree cover. On restored sites with fabaceous species, the microbial biomass is three times higher than non-restored sites, improving the rates of organic matter mineralization and restoring the catabolic diversity to the level of natural Guyanese soils. These results confirm that the establishment of fabaceous species under controlled conditions significantly improves the restoration of microbial communities in mining soils. 相似文献